Process for producing fluoropropenes

ABSTRACT

Dehydrohalogenation processes for the preparation of fluoropropenes from corresponding halopropanes, in which the fluoropropenes have the formula CF 3 CY═CX N H P , wherein X and Y are independently hydrogen or a halogen selected from fluorine, chlorine, bromine and iodine; and N and P are independently integers equal to 0, 1 or 2, provided that (N+P)=2.

BACKGROUND OF THE INVENTION

The present invention relates to a process for producing fluoropropenesin good yield on an industrial scale using commercially and readilyavailable starting materials. More particularly, the present inventionrelates to a process for producing fluoropropenes by thedehydrohalogenation of halopropanes, either by reaction with anessentially miscible alkali or alkaline earth metal hydroxide solutionin a non-alcohol solvent, or by thermal decomposition.

The production of fluoropropenes such as CF₃CH═CH₂ by catalytic vaporphase fluorination of various saturated and unsaturatedhalogen-containing C₃ compounds is described in U.S. Pat. Nos.2,889,379; 4,798,818 and 4,465,786. U.S. Pat. No. 5,532,419 discloses avapor phase catalytic process for the preparation of fluoroalkene usinga chloro- or bromo-halofluorocarbon and HF. EP 974,571 discloses thepreparation of 1,1,1,3-tetrafluoropropene by contacting1,1,1,3,3-pentafluoropropane (HFC-245fa) in the vapor phase with achromium-based catalyst at elevated temperature, or in the liquid phasewith an alcoholic solution of KOH, NaOH, Ca(OH)₂ or Mg(OH)₂.

A fluoropropene of particular interest is 1,3,3,3-tetrafluoropropene(HFC-1234ze), which has potential use as a low global warming potentialrefrigerant. However, this material is presently not available incommercial quantity. The existing technology to make HFC-1234ze is afluorination process using 1,1,1,3,3-pentachloropropane (HCC-240fa) andHF in the presence of a vapor phase catalyst. HFC-1234ze is a by-productof the reaction that is made in relatively small quantity, i.e., lessthan about 8 area % in a gas chromatograph (GC) of the organic reactionproduct.

The process is very expensive because of the low selectivity for thedesired product, HFC-1234ze. The reaction is actually intended for themanufacture of HFC-245fa, in which small quantities of HFC-1234ze isproduced as a by-product. Complicating matters, the process involveshandling large quantities of hazardous materials such as HF and HCl.

Henne et al., J. Am. Chem. Soc., 68, 496–497 (1946) described thesynthesis of various fluoropropenes from CF₃CH₂CF₃ using, e.g.,alcoholic KOH, with varying degrees of success. For example, it isstated that in some instances dehydrohalogenation was unsuccessful. Inanother instance, a protracted reaction time (3 days) was required, orrelatively low product yield (40%, 65%) was obtained.

Tarrant, et al., J. Am. Chem. Soc., 77, 2783–2786 (1955) described thesynthesis of CF₃CH═CF₂ starting with: (1)3-bromo-1,1,3,3-pentafluoropropane and reacting it with a hot solutionof KOH in water; and (2) 3-bromo-1,1,3,3-tetrafluoropropene, reacting itwith HF at 150□C and neutralizing the reaction products with a KOHsolution.

Kimura, et al., J. Org. Chem. 48, 195–198 (1983) described multi-phasedehydrohalogenation of brominated compounds using aqueous KOH and aphase transfer catalyst based on polyethylene glycols and polyethyleneglycol-grafted copolymers. The preparation of fluoropropenes by thedehydrohalogenation of fluoropropane using aqueous KOH and a phasetransfer catalyst, but with improved yields and selectivity is disclosedby U.S. Pat. No. 6,548,719.

There is a continuing need for means by which fluoropropenes can beproduced commercially with high yield and selectivity, eithercatalytically or non-catalytically.

SUMMARY OF THE INVENTION

The present invention provides two new dehydrohalogenation methods bywhich fluoropropenes may be commercially produced with high yield andselectivity. According to one aspect of the present invention, adehydrohalogenation process is provided for the preparation offluoropropenes of the formula CF₃CY═CX_(N)H_(P) wherein X and Y areindependently hydrogen or a halogen selected from the fluorine,chlorine, bromine and iodine, and N and P are independently integersequal to 0, 1 or 2, provided that (N+P)=2, in which there is reacted,without a catalyst, a halopropane of the formula:CF₃C(YR₁)C(X_(N)H_(P)R₂)wherein R₁, R₂, X and Y are independently hydrogen or a halogen selectedfrom fluorine, chlorine, bromine and iodine, provided that at least oneof R₁, R₂, X and Y is a halogen and there is at least one hydrogen andone halogen on adjacent carbon atoms; with a solution of at least onealkali or alkaline earth metal hydroxide in a non-aqueous, non-alcoholsolvent therefor that is at least essentially miscible with thehalopropane, wherein the reaction is performed at a temperature at whichdehydrohalogenation will occur.

Reactions performed without a catalyst produce cleaner reactionproducts, thereby simplifying product work-up and isolation. Thehalopropane can be CF₃CH₂CF₂H (a commercially available compound alsoknown as HFC-245fa) or CF₃CH₂CHClF (HCFC-244fa) a by-product of themanufacture of HFC-245fa. Both halopropanes will dehydrohalogenate toform HFC-1234ze.

According to another aspect of the present invention, adehydrohalogenation process is provided for the preparation offluoropropenes of the formula CF₃CY═CX_(N)H_(P), wherein X and Y areindependently hydrogen or a halogen selected from fluorine, chlorine,bromine and iodine, and N and P are independently integers equal to 0, 1or 2 provided that (N+P)=2, comprising heating to a temperature at whichdehydrohalogenation by thermal decomposition occurs a halopropane of theformula:CF₃C(YR₁)C(X_(N)H_(P)R₂)wherein R₁, R₂, X and Y are independently hydrogen or a halogen selectedfrom fluorine, chlorine, bromine and iodine, provided that at least oneof R₁, R₂, X and Y is a halogen and there is at least one hydrogen andone halogen on adjacent carbon atoms. The thermal decomposition reactioncan be performed either with or without a catalyst for hydrogen halideremoval, such as transition metal halides and oxides and combinationthereof, preferably iron halides, nickel halides, cobalt halides andcombinations thereof. HFC-245fa and CF₃CH₂CHClF (HCFC-244fa) can also bereacted by the thermal decomposition reaction of the present inventionto form HFC-1234ze.

DETAILED DESCRIPTION OF THE INVENTION

The present invention can be generally described as a process for thepreparation of fluoropropenes of the formula CF₃CY═CX_(N)H_(P) wherein Xand Y are independently a hydrogen or a halogen selected from fluorine,chlorine, bromine and iodine; and N and P are integers independentlyequal to 0, 1 or 2, provided that (N+P)=2.

Two dehydrohalogenation methods by which the fluoropropenes may beprepared are disclosed.

Both methods dehydrohalogenate a halopropane having the formula:CF₃C(YR₁)C(X_(N)H_(P)R₂)wherein R₁, R₂, X and Y are independently hydrogen or a halogen selectedfrom fluorine, chlorine, bromine and iodine, provided that at least oneof R₁, R₂, X and Y is a halogen and there is at least one hydrogen andone halogen on adjacent carbon atoms.

Included among the halopropanes that can be included in the presentinvention is 1,1,1,3,3-pentafluoropropane or HFC-245fa and1-chloro-1,3,3,3-tetrafluoropropane or HCFC-244fa. Various methods forproducing these materials are described in U.S. Pat. Nos. 5,710,352;5,969,198; 5,728,904; and 6,023,004. Another method described in U.S.Pat. No. 5,574,192 is said to be economical, amenable to large-scaleapplication and uses readily available raw materials. The process ofthat patent uses two steps as follows: (1) formation of CCl₃CH₂CHCl₂ bythe reaction of CCl₄ with vinyl chloride; and (2) conversion ofCCl₃CH₂CHCl₂ to CF₃CH₂CHF₂ and CF₃CH₂CHFCl by reaction with HF in thepresence of a fluorination catalyst selected from antimony halides,niobium halides, arsenic halides, tantalum halides; tin halides;titanium halides; antimony mixed halides; niobium mixed halides, arsenicmixed halides, tantalum mixed halides, mixed tin halides; mixed titaniumhalides and mixtures thereof. Under-fluorinated materials, such asCF₃CH₂CHCl₂, may be recycled in subsequent runs. The under-fluorinatedmaterial CF₃CH₂CHClF, or HFC-244fa, can also be used as a startingmaterial in the present invention for producing a fluoropropene. Thus,the above-described process can be utilized to obtain two differentstarting materials for the process of the present invention.

Furthermore, commercial quantities of CF₃CH₂CF₂H are available fromHoneywell International, Inc., Morristown, N.J., for use as the startingmaterial of the present process for direct conversion to thefluoroalkene CF₃CH═CFH by dehydrofluorination according to eitherprocess disclosed herein. Other useful starting materials for theproduction of fluoropropenes and/or fluorohalopropenes include thefollowing: CF₃CH₂CF₂Br; CF₃CH₂CF₂l; CF₃CHFCF₂Br; CF₃CH₂CH₂Cl;CF₃CH₂CH₂Br; CF₃CH₂CH₂l; CF₃CHBrCF₂Br; CF₃CHClCF₂Cl; CF₃CH₂CFHCl;CF₃CH₂CFHBr; CF₃CHClCF₂H; CF₃CH₂CCl₃; CF₃CH₂CF₃; and the like.

In another embodiment of the invention, HCFC-244fa and/or HFC-245fa canbe prepared by fluorinating 1,1,1,3,3-pentachloropropane(HCC-240fa). Inthis embodiment, in a preliminary step, the process of the inventioninvolves the formation of HCFC-244fa and/or HFC-245fa by reacting1,1,1,3,3-pentachloropropane (HCC-240fa) with hydrogen fluoride (HF) inthe vapor phase, or the liquid phase, preferably in the presence of afluorination catalyst as is well known in the art.

The result is a reaction product of one or both of the two products,HCFC-244fa and/or HFC-245fa. In the preferred embodiment of theinvention, the HF to HCC-240fa mole ratio preferably ranges from about2:1 to about 100:1; more preferably from about 4:1 to about 50:1 andmost preferably from about 5:1 to about 20:1.

Useful fluorination catalysts include, but are not limited to,transition metal halides, Group IVb and Vb metal halides, andcombinations thereof, preferably supported on activated carbon orfluorinated alumina. More specifically, preferred vapor phasefluorination catalysts non-exclusively include SbCl₅, SbCl₃, SbF₅,TaCl₅, SnCl₄, NbCl₅, TiCl₄, MoCl₅, Cr₂O₃, Cr₂O₃/Al₂O₃, Cr₂O₃/AlF₃,Cr₂O₃/carbon, CoCl₂/Cr₂O₃/Al₂O₃, NiCl₂/Cr₂O₃/Al₂O₃, CoCl₂/AlF₃,NiCl₂/AlF₃ and mixtures thereof. Preferred liquid phase fluorinationcatalysts non-exclusively include SbCl₅, SbCl₃, SbF₅, TaCl₅, SnCl₄,NbCl₅, TiCl₄, and MoCl₅. It is understood that after pre-treatment withHF or during reaction in the presence of HF the above mentioned catalystwill be partially fluorinated Chromium oxide/aluminum oxide catalystsare described in U.S. Pat. No. 5,155,082 which is incorporated herein byreference. Chromium (III) oxides such as crystalline chromium oxide oramorphous chromium oxide are preferred vapor phase fluorinationcatalysts with amorphous chromium oxide being the most preferred vaporphase catalyst. Chromium oxide (Cr₂O₃) is a commercially availablematerial which may be purchased in a variety of particle sizes.Unsupported SbCl₅ and SbCl₃ halides are preferred liquid phasecatalysts. Both of these liquid phase catalysts are commerciallyavailable and well known in the art. Fluorination catalysts having apurity of at least 98% are preferred. The fluorination catalyst ispresent in an amount sufficient to drive the reaction. The fluorinationreaction may be conducted in any suitable fluorination reaction vesselor reactor but it should preferably be constructed from materials whichare resistant to the corrosive effects of hydrogen fluoride such asnickel and its alloys, including Hastelloy, Inconel, Incoloy, and Monelor vessels lined with fluoropolymers.

Any water in the hydrogen fluoride (HF) will react with and deactivatethe fluorination catalyst. Therefore substantially anhydrous hydrogenfluoride is preferred. By “substantially anhydrous” it is meant that theHF contains less than about 0.05 weight % water and preferably containsless than about 0.02 weight % water. However, one of ordinary skill inthe art will appreciate that the presence of water in the HF can becompensated for by increasing the amount of catalyst used.

The liquid phase fluorination of HCC-240fa is preferably conducted at atemperature of from about 50° C. to about and 450° C., more preferablyfrom about 60° C. to about 180° C. and most preferably from about 65° C.and 150° C. Fluorination is preferably conducted at a pressure of fromabout 50 psig to about 400 psig. The reactor is preferably preheated tothe desired fluorination reaction temperature while anhydrous HF is fedto the reactor. The HCC-240fa and HF may be fed to the reactor at thedesired temperatures and pressures that are described herein. In apreferred embodiment of the invention, either or both of the HCC-240faand HF are pre-vaporized or preheated prior to entering the reactor.

When HCC-240fa and HF are reacted in a vapor phase with the fluorinationcatalyst the HCC-240fa and HF may be fed to the reactor at the desiredtemperatures and pressures that are described herein. The reactor ispreheated to the fluorination reaction temperature while anhydrous HF isfed to the reactor. The HCC-240fa and HF may be fed to the reactor atany convenient temperature and pressure. In a preferred embodimenteither or both of the HCC-240fa and HF are pre-vaporized or preheated toa temperature of from about 30° C. to about 300° C. prior to enteringthe reactor. In another embodiment, the HCC-240fa and HF are vaporizedin the reactor.

The HF and HCC-240fa feeds are then adjusted to the desired mole ratio.The HF to HCC-240fa mole ratio preferably ranges from about 2:1 to about100:1; more preferably from about 4:1 to about 50:1 and most preferablyfrom about 5:1 to about 20:1.

The fluorination reaction is conducted at a preferred temperatureranging from about 80° C. to about 400° C.; more preferably from about100° C. to about 350° C. and most preferably from about 200° C. to about330° C. Reactor pressure is not critical and can be superatmospheric,atmospheric or under vacuum. The vacuum pressure can be from about 5torr to about 760 torr. The reactant vapor is allowed to contact thefluorination catalyst for from about 0.01 to about 240 seconds, morepreferably from about 0.1 to about 60 seconds and most preferably fromabout 0.5 to about 20 seconds.

Usually the process flow of the HCC-240fa and HF is in the downdirection through a bed of the catalyst. Before each use, the catalystis preferably dried, pre-treated and activated. It may also beadvantageous to periodically regenerate the catalyst after prolonged usewhile in place in the reactor.

For Cr₂O₃, Cr₂O₃/Al₂O₃, Cr₂O₃/AlF₃, Cr₂O₃/carbon, CoCl₂/Cr₂O₃/Al₂O₃,NiCl₂/Cr₂O₃/Al₂O₃, CoCl₂/AlF₃, NiCl₂/AlF₃ catalysts, pre-treatment canbe done by heating the catalyst to about 250° C. to about 430° C. in astream of nitrogen or other inert gas. The catalyst may then beactivated by treating it with a stream of HF diluted with a large excessof nitrogen gas in order to obtain high catalyst activity. Regenerationof the catalyst may be accomplished by any means known in the art suchas, for example, by passing air or air diluted with nitrogen over thecatalyst at temperatures of from about 100° C. to about 400° C.,preferably from about 200° C. to about 375° C., for from about 1 hour toabout 3 days, depending on the size of the reactor. For SbCl₅, SbCl₃,TaCl₅, SnCl₄, NbCl₅, TlCl₄, MoCl₅ catalysts, supported on an solidsupport such as activated carbon, pre-treatment or activation can bedone by first heating the catalyst to about 30° C. to 250° C. in astream of nitrogen or other inert gas. It is then treated with a streamof HF in the absence or presence of an oxidizing agent such as chlorinegas in order to obtain high catalyst activity. In addition, the catalystmay optionally be kept active by co-feeding chlorine to the reactorduring reaction.

HCFC-244fa and HFC-245fa may be recovered from the fluorination reactionproduct mixture comprised of unreacted starting materials andby-products, including HCl, by any means known in the art, such as byscrubbing, extraction, and preferably distillation. For example, thedistillation may be preferably conducted in a standard distillationcolumn at a pressure, which is less than about 300 psig, preferably lessthan about 150 psig and most preferably less than 100 psig. The pressureof the distillation column inherently determines the distillationoperating temperature. HCl may be recovered by operating thedistillation column at from about −40° C. to about 25° C., preferablyfrom about −40° C. to about −20° C. Single or multiple distillationcolumns may be used. The distillate portion includes substantially allthe HCFC-244fa, HFC-245fa, unreacted HF and HCl produced in the reactionas well as any other impurities. In the preferred embodiment, HCFC-244faand the HFC-245fa are separated from all other reaction by-products andunreacted HF for further reaction in step (b) described herein. In thepreferred embodiment, any HF present may also be recovered and recycledback for subsequent fluorination reactions. 1234ze is formed by thedehydrochlorination of 1-chloro-1,3,3,3-tetrafluoropropane (HCFC-244fa)or the dehydrofluorination of 1,1,1,3,3-pentafluoropropane (HFC-245fa).

According to one method of the present invention, the halopropane isdehydrohalogenated with an alkali metal or alkaline earth metalhydroxide in a non-aqueous, non-alcohol solvent for the alkali metal oralkaline earth metal hydroxide that is at least partially miscible withthe halopropane. Alkali metal and alkaline earth metal hydroxidessuitable for use in the present invention include, but are not limitedto LiOH, KOH, NaOH, CaO, Ca(OH)₂, CaCO₃, and/or lime stone, and thelike. By either method, the dehydrochlorination of HCFC-244fa proceedsas follows:

The dehydrohalogenation is performed within a temperature range at whichthe halopropane will dehydrohalogenate. According to one aspect of thismethod, alkali metal or alkalin eearth metal hydroxide pellets aredissolved in the solvent with agitation under otherwise ambientconditions. The halopropane is then bubbled through the alkali metal oralkaline earth metal hydroxide solution as the temperature of thesolution is gradually increased by heating. Gradual heating is continueduntil initiation of dehydrohalogenation is observed, after which thetemperature at which dehydrohalogenation initiation occurred ismaintained until completion of the process.

In carrying out the process, the molar ratio of alkali metal or alkalineearth metal hydroxide relative to the amount of halopropane is fromabout 1:1 to about 20;1, preferably from about 1:1 to about 15:1; andmore preferably from about 1:1 to about 12:1; for example, from 1:1 toabout 10:1. In the preferred embodiment of the invention, the causticstrength of the caustic solution is from about 2 wt % to about 100 wt %,more preferably from about 5 wt % to about 90 wt % and most preferablyfrom about 10 wt % to about 80 wt %. The reaction is preferablyconducted at a temperature of from about 20° C. to about 150° C., morepreferably from about 30° C. to about 110° C. and most preferably fromabout 40° C. to about 90° C. The reaction pressure is not critical. Thereaction can be conducted at atmospheric pressure, super-atmosphericpressure or under vacuum. The vacuum pressure can be from about 5 torrto about 760 torr. Preferably, the reaction is conducted at atmosphericor super-atmospheric pressure.

The dehydrohalogenation reaction can be accomplished using a solution ofat least one alkali metal or alkaline earth metal hydroxide in a non,aqueous, non-alcohol solvent for the alkali metal or alkaline earthmetal hydroxide that is essentially miscible with the halopropane. Forpurposes of the present invention, “essentially miscible” means that anagitated mixture containing 50 wt. % halpropane and 50 wt. % solventdoes not separate to form more than one liquid phase over thetemperature range at which the dehydrohalogenation will occur, or, ifsuch separation does occur, one of the liquid phases is very small, lessthan 10 wt. % of the total weight of the blend.

Examples of non-alcohol solvents suitable for use with the presentinvention include, but not limited to, nitrites such as acetonitrile,ethers such as diethyl ether, tetrahydrofuran andperfluorotetrahydrofuran, esters such as methyl acetate and ethylacetate, amides, ketones, sulfoxides, phosphates, carboxylates, and thelike.

The alkali metal or alkaline earth metal hydroxide need not be highlysoluble in the solvent. An amount of water, alcohol, or mixture thereofmay be added to the solvent for the alkali metal or alkaline earth metalhydroxide in quantities that improve the solubility of the alkali metalor alkaline earth metal hydroxide therein. Embodiments according to thisaspect of the present invention will blend a solution of the alkalimetal or alkaline earth metal hydroxide in water, alcohol or a mixtureof water and alcohol, with the solvent. Typically, the amount of water,alcohol, or water-alcohol blend will not exceed about 50 wt. % of thetotal quantity of solvent for the alkali metal or alkaline earth metalhydroxide, and preferably will not exceed about 20 wt. %. Alcohols thatmay be used contain from 1 to 5 carbon atoms, and preferably from 1 to 3carbon atoms.

Solvents are selected that are at least partially miscible with thealkali metal or alkaline earth metal hydroxide solution, which may be inwater, alcohol or a mixture thereof. For purposes of the presentinvention “partially miscible” means a level of miscibility that permitsthe solvent to dissolve in the alkali metal or alkaline earth metalhydroxide solution to the extent that the dehydrohalogenation reactionwill occur upon contact of the halopropane therewith the blend. A highdegree is miscibility is not required in order for the reaction toproceed at the interface of the solvent and alkali metal or alkalineearth metal hydroxide solution. More caustic will dissolve as the amountin solution is depleted by the dehydrohalogenation reaction. The solventneed only be at least about 1%, preferably at least about 5%, and morepreferably at least 10% soluble, the alkali metal or alkaline earthmetal hydroxide solution on a weight basis.

In an alternate embodiment of the invention, the dehydrochlorination ofHCFC-244fa and dehydrofluorination of HFC-245fa may be done by thermaldecomposition in the presence or in the absence of a catalyst. Suitablecatalysts include transition metal halides and oxides, supported orbulk. Preferred catalysts include, but not limited to, FeCl₂, FeCl₃,NiCl₂, CoCl₂, supported or in bulk. The preferred temperatures for thethermal decomposition are from about 30° C. to about 400° C., morepreferably from about 50° C. to about 350° C. and most preferably fromabout 75° C. to about 300° C. As above, the reaction is preferablyconducted at atmospheric pressure, super-atmospheric pressure. Reactionunder vacuum is also acceptable. The vacuum pressure can be from about 5torr to about 760 torr.

The reactions may be conducted in any suitable reactor. Further, thedehydrochlorination of HCFC-244fa and the dehydrofluorination ofHFC-245fa may either be conducted simultaneously in the same reactor, orthey may first be separated followed by separately dehydrochlorinatingHCFC-244fa with the caustic solution or by thermal decomposition andseparately dehydrofluorinating HFC-245fa with the caustic solution or bythermal decomposition. The result of this two step process is a highyield of HFC-1234ze.

Therefore, according to preferred embodiments of the invention, thedehydrochlorination of HCFC-244fa and dehydrofluorination of HFC-245faare accomplished either by thermal decomposition or by reacting thesewith a strong caustic solution at an elevated temperature. By eithermethod, the dehydrochlorination of HCFC-244fa proceeds as follows:

Furthermore, by either method, the dehydrofluorination of HFC-245faproceeds as follows:

Both the dehydrochlorination of HCFC-244fa and dehydrofluorination ofHFC-245fa are achieved according to the present invention by usingcaustic for hydrogen halide removal or by thermal decomposition in theabsence of a catalyst or with a catalyst selected from transition metalhalides and oxides and combinations thereof, preferably iron halides,nickel halides, cobalt halides and combinations thereof.

Both processes described herein are useful for the preparation offluoropropenes and/or fluorohalopropenes having the following formula:CF₃CY═CX_(N)H_(P)wherein X and Y and independently hydrogen or a halogen selected fromfluorine, chlorine, bromine and iodine; and N and P are integersindependently equal to 0, 1 or 2, provided that (N+P)=2. Such compoundsinclude CF₃CH═CF₂,CF₃CH═CFH, CF₃CBr═CF₂, CF₃CH═CH₂, CF₃CF═CF₂,CF₃CCl═CF₂, CF₃CF═CClF, CF₃CCl═CHF, CF₃CH═CHCl, CF₃CCl═CClF, CF₃CH═CCl₂,CF₃CF═CCl_(.2), and the like. The fluoropropenes prepared by bothmethods of this invention are readily recovered by any means known inthe art, such as by scrubbing, extraction, and preferably distillation.Depending on extent of conversion of the starting material, the productcan be used directly or further purified by standard distillationtechniques. Unreacted halopropane and certain reaction by-products canbe recycled back to the reaction vessel to provide a continuous process.Alternatively, fresh halopropane may be supplied to the reaction mixturein order to run the process continuously.

The fluoropropenes obtained by the inventive processes are useful asmonomers for producing fluorine-containing oligomers, homopolymers andcopolymers, as well as intermediates for other fluorine-containingindustrial chemicals.

The following examples are given as specific illustrations of theinvention. It should be understood, however, that the invention is notlimited to these specific details set forth in the examples. All partsand percentages in the examples, as well as in the remainder of thespecification, are by weight unless otherwise specified.

Further, any range of numbers recited in this specification orparagraphs hereinafter describing or claiming various aspects of theinvention, such as that representing a particular set of properties,units of measure, conditions, physical states or percentages, isintended to literally incorporate expressly herein by reference orotherwise, any number falling within such range, including any subset ofnumbers or ranges subsumed within any range so recited. The term “about”when used as a modifier for, or in conjunction with, a variable, isintended to convey that the numbers and ranges disclosed herein areflexible and that practice of the present invention by those skilled inthe art using temperatures, concentrations, amounts, contents, carbonnumbers, and properties that are outside of the range or different froma single value, will achieve the desired result, namely, processes forthe preparation of fluoropropenes and reactants used in such processes.

EXAMPLES Example 1

To a reaction setup consisting of a 3-neck round bottom flask (5 L),mechanical agitator, reflux condenser, and low temperature cold trap wasadded to 3000 ml acetonitrile and 9.9 moles (504 g) of KOH pellets.After mixing, 5.1 moles (684 g) of HFC-245fa were added through a diptube. The reagents were heated slowly with vigorous agitation. Reactionwas observed at about 60° C. The crude product was collected in the coldfinger. The crude material was analyzed by GC and consisted of a goodyield of HFC-1234ze.

Example 2

Example 1 is repeated except 5 moles (752 grams) of HCFC 244fa is addedto the acetonitrile/caustic solution through the dip tube. The reagentswere heated slowly with vigorous agitation. Reaction is observed atslightly lower temperatures than in Example 1. The crude product iscollected in the cold finger. The crude material collected consisted ofa good yield of HFC-1234ze.

Example 3

A 50 gal. Fluoropolymer lined reactor was charged with 75 lbs of liquidSbCl₅ fluorination catalyst. The reactor was equipped with a 6″ D×8′ Lcatalyst stripper containing structured packing and reflux condenser.The catalyst was first fluorinated by adding a sufficient amount ofHydrogen Fluoride (HF). The reactor was heated to 80–95° C. and broughtto a pressure of 150–180 psig. Gaseous HF was fed to the reactorcontinuously at a rate of 23–28 lb/hr through a sparger and liquid1,1,1,3,3-pentachloropropane (HCC-240fa) was fed continuously at a rateof 40–50 lb/hr. Cl₂ was continuously added to the reaction mixture tokeep the catalyst active at 1.5–2.0 lb/hr. The gas exiting the refluxcondenser was passed through a scrubber that contained KOH solution toremove excess HF and the HCl that was generated during the reaction.Several thousand lbs of the crude product was collected after thescrubber and was analyzed by GC. The following is the analysis of themajor component of the crude product in GC area %. Note the presence ofthe HFC1234ze after the material was passed through the scrubbercontaining KOH solution.

Component GC area % G1234 0.1157 245fa 92.7560 1233zd 0.1269 244fa3.3879 243fa 1.6298 Others 1.9837

Example 4

About 132 g (about 1.33 g/cc bulk density) of a chromium (III) oxidecatalyst was charged to a reactor of 1″ diameter Monel pipe. Thecatalyst was dried and pretreated with HF before use. The reactor waspreheated to the reaction temperature of about 300° C. while anhydrousHF was fed to the reactor. An organic feed (HCC-240) was started whenthe reactor reached the desired temperature and pressure. The HF andorganic feeds were then adjusted to the desired rates. HCFC-244fa andHFC-245fa were found in the reactor effluent product stream, along withother partially fluorinated species such as 1233zd, 1234ze and 243fa.

Example 5

In a typical experiment, a 2.54 cm×81 cm Monel® reactor is used. About500 ml of FeCl₃ catalyst supported on activated carbon was packed intothe reactor. The reactor was heated to 150° C. under 1 liter/hr ofnitrogen flow to dry the catalyst for 4 hours. Then, the reactortemperature is brought to 250° C. under the same nitrogen flow and 244fais fed to the reactor at 1 g/min, and in the mean time the nitrogen flowis stopped. HFC-1234ze was found by using the in-line GC at the outletof the reactor at 98% selectivity and 95% single pass conversion.

Example 6

The same experiment described in Example 5 is repeated, except that245fa is used as feed. At the outlet of the reactor, 1234ze is found at95% selectivity and 85% single pass conversion.

The principles, preferred embodiments, and modes of operation of thepresent invention have been described in the foregoing specification.The invention which is intended to be protected herein, however, is notto be construed as limited to the particular forms disclosed, sincethese are to be regarded as illustrative rather than restrictive.Variations and changes may be made by those skilled in the art, withoutdeparting from the spirit of the invention.

1. A dehydrohalogenation process for the preparation of fluoropropenesof the formula CF₃CY═CX_(N)H_(P), wherein X and Y are independentlyhydrogen or a halogen selected from the group consisting of fluorine,chlorine, bromine and iodine; and N and P are independently integersequal to 0,1 or 2, provided that (N+P)=2; comprising reacting without acatalyst, a halopropane of the formula:CF₃C(YR₁)C(X_(N)H_(P)R₂) wherein R₁, R₂, X and Y are independentlyhydrogen or a halogen selected from the group consisting of fluorine,chlorine, bromine and iodine, provided that at least one of R₁, R₂, Xand Y is a halogen and there is at least one hydrogen and one halogen onadjacent carbon atoms; with a caustic solution of at least one alkalimetal or alkaline earth metal hydroxide in a non-aqueous, non-alcoholsolvent for said alkali metal or alkaline earth metal hydroxide that isessentially miscible with said halopropane, wherein the reaction isperformed within a temperature range at which dehydrohalogenation willoccur.
 2. The process of claim 1 wherein the reactant comprises1-chloro-1,3,3,3-tetrafluoropropane.
 3. The process of claim 1 whereinthe reactant comprises 1,1,1,3,3-pentafluoropropane.
 4. The process ofclaim 1 wherein the reactant comprises both1-chloro-1,3,3,3-tetrafluoropropane and 1,1,1,3,3-pentafluoropropane. 5.The process of claim 1 wherein said caustic solution comprises LiOH,NaOH, KOH, CaO, Ca(OH)₂, CaCO₃, lime stone or combinations thereof. 6.The process of claim 1, wherein said caustic solution solvent isselected from the group consisting of nitriles, ethers, esters, amides,ketones, sulfoxides, phosphates,carboxylates, and combinations of two ormore of these.
 7. The process of claim 1, wherein said caustic solutionsolvent comprises acetonitrile.
 8. The process of claim 1, wherein saidcaustic solution solvent comprises diethyl ether.
 9. The process ofclaim 1, wherein said caustic solution solvent comprisestetrahydrofuran.
 10. The process of claim 1, wherein said causticsolution solvent comprises perfluorotetrahydrofuran.
 11. The process ofclaim 1, wherein said caustic solution solvent comprises methyl acetate.12. The process of claim 1, wherein said caustic solution solventcomprises ethyl acetate.
 13. The process of claim 4 wherein saiddehydrohalogenation of said 1-chloro-1,3,3,3-tetrafluoropropane and1,1,1,3,3-pentafluoropropane are conducted simultaneously in the samereactor.
 14. The process of claim 1 wherein the reaction is conducted ata temperature of from about 20° C. to about 150° C.
 15. The process ofclaim 1 wherein the reaction is conducted at atmospheric pressure orunder vacuum.
 16. The process or claim 1 wherein the reaction isconducted at superatmospheric pressure.
 17. The process of claim 1wherein the caustic strength of said caustic solution is from about 2 wt% to about 100 wt %.
 18. The process of claim 1, wherein the molar ratioof caustic to halopropane is about 1:1 to about 20:1.
 19. The process ofclaim 1 wherein the reactant comprises1-chloro-1,3,3,3-tetrafluoropropane and/or1,1,1,3,3-pentafluoropropane,and wherein said reactant is previouslyprepared by fluorinating 1,1,1,3,3-pentachloropropane with hydrogenfluoride in a vapor phase in the presence of a fluorination catalyst.20. The process of claim 19 wherein said fluorination catalyst isselected from the group consisting of transition metal halides, GroupIVb metal halides, Group Vb metal halides and combinations thereof onactivated carbon or fluorinated alumina.
 21. The process of claim 19wherein said fluorination catalyst is selected from the group consistingof SbCl₅, SbCl₃, SbF₅, TaCl₅, SnCl₄, NbCl₅, TiCl₄, MoCl₅, Cr₂O₃,Cr₂O₃/Al₂O₃, Cr₂O₃/AlF₃, Cr₂O₃/carbon, CoCl₂/Cr₂O₃/Al₂O₃,NiCl₂/Cr₂O₃/Al₂O₃, CoCl₂/AlF₃, NiCl₂/AlF₃and combinations thereof. 22.The process of claim 19 wherein said fluorination catalyst is selectedfrom the group consisting of Cr₂O₃, Cr₂O₃/carbon, Cr₂O₃/AlF₃,CoCl₂/AlF₃,NiCl₂/AlF₃and combinations thereof.
 23. The process of claim 19 whereinsaid fluorination catalyst comprises SbCl₃ or SbCl₅ supported onactivated carbon.
 24. The process of claim 1 wherein the reactantcomprises 1-chloro-1,3,3,3-tetrafluoropropane and/or1,1,1,3,3-pentafluoropropane, and wherein said reactant is previouslyprepared by fluorinating 1,1,1,3,3-pentachloropropane with hydrogenfluoride in a liquid phase in the presence of a fluorination catalyst.25. The process of claim 24 wherein said fluorination catalyst isselected from the group consisting of transition metal halides, GroupIVb metal halides, Group Vb metal halides and combinations thereof. 26.The process of claim 24 wherein said fluorination catalyst is selectedfrom the group consisting of SbCl₅, SbCl₃, SbF₅, TaCl_(5, SnCl) ₄,NbCl₅, TiCl₄, MoCl₅, and combinations thereof.
 27. The process of claim24 wherein said fluorination catalyst is selected from the groupconsisting of SbCl₅, SbCl₃ and combinations thereof.
 28. The process ofclaim 19 wherein the fluorination is conducted at a temperature of fromabout 100° C. to about 350° C.
 29. The process of claim 19 wherein thefluorination is conducted at atmospheric pressure or under vacuum. 30.The process of claim 29, wherein the fluorination is conducted undervacuum pressure between about 5 and about 760 torr.
 31. The process ofclaim 19, wherein said fluorination is conducted at superatmosphericpressure.
 32. The process of claim 19 wherein the mole ratio of hydrogenfluoride to 1,1,1,3,3-pentachloropropane is from about 2:1 to about100:1.
 33. The process of claim 19 further comprising feeding chlorineto the fluorination reaction to keep the fluorination catalyst active.34. The process of claim 24 wherein the fluorinating is conducted at atemperature of from about 60° C. to about 180° C.
 35. The process ofclaim 24 wherein the fluorinating is conducted at a pressure of fromabout 50 psig and 400 psig.
 36. The process of claim 24 wherein the moleratio of hydrogen fluoride to 1,1,1,3,3-pentachloropropane is from about2:1 to about 100:1.
 37. The process of claim 24 further comprisingfeeding chlorine to the fluorination reaction to keep the fluorinationcatalyst active.
 38. A dehydrohalogenation process for the preparationof fluoropropenes of the formula CF₃CY═CX_(N)H_(P), wherein X and Y areindependently hydrogen or a halogen selected from the group consistingof fluorine, chlorine, bromine and iodine, and N and P are independentlyintegers equal to 0, 1 or 2, provided that (N+P)=2; comprising heatingto a temperature at which dehydrohalogenation by thermal decompositionoccurs, a halopropane of the formula:CF₃C(YR₁)C(X_(N)H_(P)R₂) wherein R₁, R₂, X and Y are independentlyhydrogen or a halogen selected from the group consisting of fluorine,chlorine, bromine and iodine, provided that at least one of R₁, R₂, Xand Y is a halogen and there is at least one hydrogen and one halogen onadjacent carbon atoms; wherein said decomposing is conducted without acatalyst.
 39. A process for the manufacture of1,3,3,3-tetrafluoropropene comprising thermally decomposing a reactantcomprising at least one of 1-chloro-1,3,3,3-tetrafluoropropane and1,1,3,3,3-pentafluoropropane, under conditions sufficient to dehydrochlorinate 1-chloro-1,3,3,3-tetrafluoropropane and/or todehydrofluorinate 1,1,1,3,3-pentafluoropropane, to form a reactionproduct which comprises 1,3,3,3-tetrafluoropropene; wherein saiddecomposing is conducted without a catalyst.
 40. A process for themanufacture of 1,3,3,3-tetrafluoropropene comprising thermallydecomposing a reactant comprising at least one of1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropane,under conditions sufficient to dehydrochlorinate1-chloro-1,3,3,3-tetrafluoropropane and/or to dehydrofluorinate1,1,1,3,3-pentafluoropropane, to form a reaction product which comprises1,3,3,3-tetrafluoropropene; wherein said decomposing is conducted in thepresence of one or more transition metal halide catalysts, wherein saidtransition metal is selected from the group consisting of iron, nickel,cobalt, and combinations thereof.
 41. The process of claim 40, thecatalyst is selected from, a group consisting of iron halides, nickelhalides, cobalt halides and combinations thereof.
 42. The process ofclaim 39 wherein 1-chloro-1,3,3,3-tetrafluoropropane isdehydrochlorinated to form a reaction product which comprises1,3,3,3-tetrafluoropropene.
 43. The process of claim 39 wherein1,1,3,3,3-pentafluoropropane is dehydrofluorinated to form a reactionproduct which comprises 1,3,3,3-tetrafluoropropene.
 44. The process ofclaim 39 wherein said dehydrochlorination of1-chloro-1,3,3,3-tetrafluoropropane and said dehydrofluorination of1,1,1,3,3,-pentafluoropropane are conducted simultaneously in the samereactor.
 45. The process of claim 39 which is conducted at a temperatureof from about 30° C. to about 400° C.
 46. The process of claim 39 whichis conducted at a temperature of from about 50° C. to about 350° C. 47.The process of claim 39 which is conducted at a temperature of fromabout 75° C. to about 300° C.
 48. The process of claim 39 which isconducted at atmospheric pressure or under vacuum.
 49. The process ofclaim 39 which is conducted a superatmospheric pressure.
 50. Adehydrohalogenation process for the preparation of fluoropropenes of theformula CF₃CY═CX_(N)H_(P), wherein X and Y are independently hydrogen ora halogen selected from the group consisting of fluorine, chlorine,bromine and iodine, and N and P are independently integers equal to 0, 1or 2, provided that (N+P)=2; comprising heating to a temperature atwhich dehydrohalogenation by thermal decomposition occurs, a halopropaneof the formula:CF₃C(YR₁)C(X_(N)H_(P)R₂) wherein R₁, R₂, X and Y are independentlyhydrogen or a halogen selected from the group consisting of fluorine,chlorine, bromine and iodine, provided that least one of R₁, R₂, X and Yis a halogen and there is at least one hydrogen and one halogen onadjacent carbon atoms; wherein said decomposing is conducted in thepresence of a transition metal halide catalyst wherein said transitionmetal is selected from the group consisting of iron, nickel, cobalt, andcombinations thereof.
 51. The process of claim 50 wherein the catalystis supported or bulk transition metal halides.
 52. The process of claim51 wherein said catalyst comprises supported or bulk FeCl₂, FeCl₃, NiCl₂or CoCl_(2.)
 53. The process of claim 39 wherein the1-chloro-1,3,3,3-tetrafluoropropane and/or 1,1,1,3,3-pentafluoropropaneare previously prepared by fluorinating 1,1,1,3,3-pentachloropropanewith hydrogen fluoride in the vapor phase in the presence of afluorination catalyst.
 54. The process of claim 53 wherein saidfluorination catalyst is selected from the group consisting oftransition metal halides, Group IVb metal halides, Group Vb metalhalides and combinations thereof on activated carbon or fluorinatedalumina.
 55. The process of claim 53 wherein said fluorination catalystis selected from the group consisting of SbCl₅, SbCl₃, SbF₅, TaCl₅,SnCl₄, NbCl₅, TiCl₄, MoCl₅, Cr₂O₃, Cr₂O₃/Al₂O₃, Cr₂O₃/AlF₃, Cr₂O₃carbon,CoCl₂/Cr₂O₃/Al₂O₃, NiCl₂/Cr₂O₃/Al₂O₃, CoCl₂/AlF₃, NiCl₂/AlF₃ andcombinations thereof.
 56. The process of claim 53 wherein saidfluorination catalyst is selected from the group consisting of Cr₂O₃,Cr₂O₃/carbon, Cr₂O₃/AlF₃, CoCl₂/AlF₃, NiCl₂/AlF₃ and combinationsthereof.
 57. The process of claim 53 wherein said fluorination catalystcomprises SbCl₃ or SbCl₅ supported on activated carbon.
 58. The processof claim 53 wherein the fluorinating is conducted at a temperature offrom about 100° C. to about 350° C.
 59. The process of claim 53 whereinthe fluorinating is conducted at atmospheric pressure or under vacuum.60. The process of claim 53 wherein the fluorinating is conducted atsuperatmospheric pressure.
 61. The process of claim 53 wherein the moleratio of hydrogen fluoride to 1,1,1,3,3-pentachloropropane is from about2:1 to about 100:1.
 62. The process of claim 53 further comprisingfeeding chlorine to the fluorinating reaction to keep the fluorinationcatalyst active.
 63. The process of claim 39 wherein the1-chloro-1,3,3,3-tetrafluoropropane and/or 1,1,1,3,3-pentafluoropropaneare previously prepared by fluorinating 1,1,1,3,3-pentachloropropanewith hydrogen fluoride in a liquid phase in the presence of afluorination catalyst.
 64. The process of claim 63 wherein saidfluorination catalyst is selected from the group consisting oftransition metal halides, Group IVb metal halides, Group Vb metalhalides and combinations thereof.
 65. The process of claim 64 whereinsaid fluorination catalyst is selected from the group consisting ofSbCl₅, SbCl₃, SbF₅, TaCl₅, SnCl₄, NbCl₅, TiCl₄, MoCl₅, and combinationsthereof.
 66. The process of claim 65 wherein said fluorination catalystis selected from the group consisting of SbCl₅, SbCl₃ and combinationsthereof.
 67. The process of claim 63 wherein the fluorinating isconducted at a temperature of from about 60° C. to about 180° C.
 68. Theprocess of claim 63 wherein the fluorinating is conducted at a pressureof from about 50 psig and 400 psig.
 69. The process of claim 63 whereinthe mole ratio of hydrogen fluoride to 1,1,1,3,3-pentachloropropane isfrom about 2:1 to about 100:1.
 70. The process of claim 63 furthercomprising feeding chlorine to the fluorinating reaction to keep thefluorination catalyst active.
 71. The process of claim 1, wherein saidcaustic solution further comprises a 1 to 5 carbon atom alcohol in anamount that is at least partially miscible with said caustic solutionsolvent.
 72. The process of claim 1, wherein said caustic solutionfurther comprises water in an amount that is at least partially misciblewith said caustic solution solvent.
 73. The process of claim 1,conducted in a continuous manner.
 74. The process of claim 38, whereinsaid process is conducted in a continuous manner.
 75. A process for themanufacture of 1,3,3,3-tetrafluoropropene comprising thermallydecomposing substantially simultaneously a reactant comprising1-chloro-1,3,3,3-tetrafluoropropane and 1,1,3,3,3-pentafluoropropaneunder conditions sufficient to dehydrochlorinate at least a portion ofsaid 1-chloro-1,3,3,3-tetrafluoropropane and to dehydrofluorinate atleast a portion of 1,1,1,3,3-pentafluoropropane, to form a reactionproduct comprising 1,3,3,3-tetrafluoropropene.
 76. A process for themanufacture of 1,3,3,3-tetrafluoropropene comprising thermallydecomposing in the presence of a catalyst a reactant comprising at leastone of 1-chloro-1,3,3,3-tetrafluoropropane and1,1,3,3,3-pentafluoropropane under conditions sufficient todehydrohalogenate at least a portion of said reactant to form a reactionproduct comprising 1,3,3,3-tetrafluoropropene.